Sodium Hydroxide → 2-Hydroxy-4-[2-({[1-phenylethylidene]amino}oxy)ethoxy]benzoic acid

HRID 29648Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 29648
[C:1]1([C:7](=[N:9][OH:10])[CH3:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C[O:12][C:13](=[O:25])[C:14]1[CH:19]=[CH:18][C:17]([O:20][CH2:21][CH2:22]Br)=[CH:16][C:15]=1[OH:24].[OH-].[Na+]>O1CCCC1.[I-].C([N+](CCCC)(CCCC)CCCC)CCC>[OH:24][C:15]1[CH:16]=[C:17]([O:20][CH2:21][CH2:22][O:10][N:9]=[C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH3:8])[CH:18]=[CH:19][C:14]=1[C:13]([OH:25])=[O:12]

Komponenten

6

Edukt 3

HCID 14798Sodium HydroxideHCID 69185AcetophenonoximeHCID 574195214-(2-Bromo-ethoxy)-2-hydroxy-benzoic acid methyl ester

Produkt 1

HCID 860393012-Hydroxy-4-[2-({[1-phenylethylidene]amino}oxy)ethoxy]benzoic acidAusbeute 27 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 67553Tetrabutylammonium IodideKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of 1-phenyl-ethanone oxime (1.156 g, 8.55 mmol) in tetrahydrofuran (75 mL) was added 4-(2-bromo-ethoxy)-2-hydroxy-benzoic acid methyl ester (2.346 g, 8.52 mmol), tetrabutylammonium iodide (0.968 g, 2.62 mmol) and 15% sodium hydroxide solution (30 mL). The reaction was heated at reflux overnight, cooled to room temperature and the layers were separated. The aqueous layer was neutralized to pH 7 by the addition of concentrated hydrochloric acid and extracted with ethyl acetate. The combined organics were washed with brine, dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue was purified by flash chromatography using ethyl acetate/hexanes (25/75)+1% formic acid to afford 2-hydroxy-4-[2-(1-phenyl-ethylideneaminooxy)-ethoxy]-benzoic acid (0.712 g, 27%) as a white solid. mp=149.1-150.4° C.; mass spectrum (+APCI, M+H) m/z 316. 1H NMR (400 MHz, DMSO-d6); δ 13.60 (bs, 1H), 11.50 (bs, 1H), 7.66 (m, 3H), 7.39 (m, 3H), 6.53 (m, 2H), 4.44 (t, 2H), 4.31 (t, 2H), 2.17 (s, 3H). Elemental analysis: Calcd. for C17H17NO5: C, 67.7; H, 5.43; N, 4.44, Found: C, 64.45; H, 5.32; N, 4.42.

Aufarbeitung

  1. temperatureThe reaction was heated
  2. temperatureat reflux overnight
  3. customthe layers were separated
  4. additionThe aqueous layer was neutralized to pH 7 by the addition of concentrated hydrochloric acid
  5. extractionextracted with ethyl acetate
  6. washThe combined organics were washed with brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash chromatography

Quellen und Nachweise

ORD-Eintrag
ord-6fdbcbd94e574cbe9609207ad1def98e
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07420083B2

Notizen zur Reaktion

Wird geladen…